Abstract
Fluorescence decays of benzosultine and naphthosultine excited at 263 nm are detected with time-correlated single-photon counting (TCSPC). Both molecules display biexponential decay with a rapid component (time constants 90 and 350 ps for benzosultine and naphthosultine, respectively) assigned to an electronically excited state S n at high energy and the slow one (constants 7.5 and 9.0 ns for benzosultine and naphthosultine, respectively) to the S 1 state. Dissociation of both molecules was investigated with nanosecond laser flash photolysis combined with transient absorption to detect the intermediates and products. With excitation at 266 nm, benzosultine yields a transient with absorption maximum at λ max = 370 nm; this transient has a short-lived component with lifetime around 1 μs and a long-lived component. Both components are insensitive to molecular oxygen. The short-lived component is tentatively assigned to the dissociation intermediate and the long-lived to be singlet o-benzoquinodimethane (o-BQDM). Photolysis of naphthosultine yields two transient species with absorption at λ max = 420 and 520 nm; we assign the former band to triplet-triplet absorption of naphthosultine and the latter to absorption by the product singlet o-naphthoquinodimethane. Optimal geometries, energetics, and vertical transitions of benzosultine, naphthosultine, o-benzoquinodimethane, and o-naphthoquinodimethane are calculated using methods based on density-functional theory (B3LYP/6-311++G**) and time-dependent density-functional theory (TD-DFT). The results of these calculations imply that the ground electronic state of these two o-quinodimethanes (o-QDM) is singlet with a structure of diene form. Their triplet states display a biradical structure. The energy separation between singlet and triplet states of o-benzoquinodimethane is calculated to be ca. 93.6 kJ/mol, but for o-naphthoquinodimethane, it is only ca. 27.8 kJ/mol. © 2004 Elsevier B.V. All rights reserved.